Polysulphonates of aromatic polyalkylene ethers



Patented Feb, 8, i938 UNITED STATES- PATENT OFFICE POLYSULPHONATES OFAROMATIC POLY- ALKYLENE ETHEBS Herman A. Bruson, Philadelphia, Pa,assignor to Riihm & Haas Company, Philadelphia, Pa.

No Drawing. Application January 12, 1937, Serial No. 120,180

10 Claims. (Cl. 260-150) This invention relates to sulphonatedaryloxyphuric acid, or with sulphur trioxide, at a low polyalkyleneethers which contain at least two temperature to 40 C.) so as to form amonosulphonic acid groups, one'of which is attached to or polysulphonicacid. After neutralizing with a carbon atom of the alkylene groupsituated caustic alkali, ammonia, amines, or any other farthest from thearomatic ring, and the others water-soluble base, an aqueous solution ofthe 5 are attached to the aromatic nucleus. These product is heated witha molecularly equivalent new compounds in their acid form have thegenquantity of a water-soluble metal sulphite at eral formula 130-190 C.for several hours, whereby the terminal halogen atom is replaced by anSOaM group ARO(CnH2a0)rCnH2n-SO3H where M is the metal. The order inwhich the 10 sulphonic groups are introduced can be reversed (3033)" byreacting the complex ether chloride with sodium sulphite first and thensulphonating the Where R is an ammauc ring, Preferably of the aromaticnucleus by the methods above indicated. benzene or naphthalene series,that can contain That procedure has the di advantage however a nuclearsubstituent A" which is a member of that it necessitates drying theSodium sulphlt the group consisting of hydrocarbon, acyl, alkreactionproduct prior to sulphonatihg the 0x5, halogen and h ff is an maticnucleus. Instead of the chloroether, the alkylene 8 D in which n 15greater than and corresponding bromoor iodo ethers can be used, in whichat least 2 carbon atoms separate alterbut, of course, with no advantageg Oxygen atoms is 1 to 2; The products obtained are extremely waterand 1is equal to 1 or soluble and give no precipitate with hard water. Theabove acidsin form of their water They are resistant to hot, boiling,dilute acids or soluble alkali metal-, ammonium-, or amine salts alkans,and are unusually efiective capillarywhel'e R is benzene naphthalene andA is active materials at extremely low concentrations. an aliphaticchain having four or more carbon Among typical ethers which give th tatoms, show marked capillary activity in aqueous ful eapmary aet1vecompounds t at d csolutions and are useful as textile assistants,discording to this invention, the following are th persing, cleansing,emulsifyin We ti intromost important: tying and spreading agents.Particularly effective for these purposes are those water-solublei:fkjgjgjggiggjgjgggggfh salts in which A is an alkyl or aliphatic acylrada. A--R--0-CIlr-CHOCHCHC1 ical having from 8 to 18 carbon atomsinclusive. E

This a lication is a continuation-inart of my gg application serial 86 2med wherein R is a phenyl group and A is an alkyl 86 June 20 1936radical or aliphatic acyl group containmg'from In Practicing theinvention compounds of the eight to eighteen carbon atoms inclusive.above type are, for practical reasons, preferabl These are obtained byheating the correspondmade by first sulphonating the aromatic nucleus mgalkyl! or acyl phenols- A ROH with an R of a monochlomryloxypolyalkylene ether haw cess of one of the following dichloroethers, re-

40 mg the formula spectively in the presence of caustic alkali, so 40 aas to etheritfy only one end of the chain: A-a-o-(c.r1=,.-o- Penna-c1 hether ClCzH4'OC2H4Cl neutralizing the sulphonic acid formed with analkali, ammonia or an amine! and subsequently 2.B-chlordethoxy-p'-chlorodiethyl ether, 45 heating an aqueous solution ofthis product with C1C2H4O-C2H40C2H4cl sodium sulphite, preferably underpressure. The d1 sulphonation of the nucleus R is carried out withchlorodusopmpyl ether chlorsulphonic acid, concentrated or fuming sul-CICH2CH(CH3) -O(CH3)CHCH2C1 5 Such monochloraryloxy-polyalkylene ethersand their process of preparation are described in my copending patentapplications Serial No. 79,718 filed May 14, 1936, and No. 82,183 filedMay 28, 1936.

The following examples are given to illustrate the invention. It is not,however, limited to the exact reagents, time, temperature and conditionsof operation shown, as it may otherwise be practiced within the scope ofthe appended claims.

Example 1 S OaM (a) To 156 g. of fl-(p-a,a,'-tetramethylbutylphenoxy)-5'chlorodiethyl ether there is added,

while stirring and cooling to about 5 C., 59 g. of chlorsulphonic acid.The mixture is stirred for oH.1-Qo-om-om-o-omom-o-om-om-solNa OsNa 4 to5 hours at 5 to 10 C. and then allowed to come to room temperature andstirred for 3 hours longer until evolution of hydrogen chloride ceasesand a sample of the product is soluble in water. The red, viscous sirupof the sulphonated chloroether thus obtained is neutralized with a 10%aqueous sodium hydroxide solution to pH 7.5.

This solution is mixed with 66 g. of anhydrous sodium sulphite (95.3%purity) and 250 cc. of water, and heated in an iron autoclave at180-190'C. for six to seven hours. Any traces of sulphite are thendestroyed by the careful addition of dilute hydrochloric acid andwarming until sulphur dioxide is no longer detectable. The solutionobtained is then filtered to remove traces of iron. The clear, paleyellow filtrate obtained is then adjusted to pH 7.5. It is an extremelypowerful dispersing agent for colloidal sulphur, and certain dyes. Itgives no precipitate with a 5% solution of calcium chloride, magnesiumsulphate, alum, or ferric chloride. It readily disperses freshlyprecipitated calcium soaps of oleic, palmitic and stearic acids. The drysolid compound may be obtained by evaporating the water, as for example,by spray-drying. It forms a white powder which dissolves readily inwater to give clear, foamy, soapy solutions. These solutions show gooddetergent properties and are stable to dilute acids and alkalies.

The p- (p-a,w -tetramethylbutylphenoxy) -B' chlorodiethyl ether used inthe above example is obtained by heatingp-a,a,'y,'y-tetramethylbutylphenol (1 mol.) with p,p'-dichlordiethylether (3 mols) and a 50% sodium hydroxide solution containing 1.17 molsof sodium hydroxide for 8 hours at -115 C., with constant stirring,filtering off NaCl, and distilling the product. It is a colorless oilboiling at 1'77 to 178 C./4 mm.

Instead of neutralizing the sulphonic acid with sodium hydroxidesolution, potassium hydroxide, sodium or potassium carbonate, ammoniumhydroxide, methylamines, or mono-, di-, or triethanolamine may be used.Potassium sulphite can be used in place of sodium sulphite, if desired.

(6) The ,9 (pt1,d,'Y,'Y tetramethylbutylphenoxy) -,9'-chlorodiethylether may be replaced in the above example by any of the followingethers toyield analogous products.

1. p- (sec-octylphenoxy) -p'-chlorodiethyl ether,

3. ,3-(n-octylphenoxy) -fr-chiorodiethyl ether,

made from n-octyl-phenol and fl, 3dichlorodiethyl ether.

Example 2 To 173 g. of p-(px,' ,y-tetramethylbutylphenoxyethoxy)-B'-chlorodiethyl ether there is added, while stirring and cooling to 20C., 55 g. of 98% sulphuric acid. The mixture is stirred for ten hours,during which time the temperature is held at 45 to.50 C. The thick oilobtained is neutralized with 10% caustic soda solution and then heatedin an autoclave with 66 g. of anhydrous sodium sulphite (95.3% purity)and 270 cc. of water for eight hours at to C., at a pressure of 140 to150 lbs. per square inch.

The soap-like solution obtained is a good detergent and emulsifyingagent. The dried product is a white powder which is extremely soluble inwater to give a foamy solution.

The 5 (p-a,a,"y,'y tetramethylbutylphenoxyethoxy) -fl'-chlorodiethylether used in the above example is made from p-a,a,-,'y-tetramethylbutylphenol, caustic soda, andfi-chloroethoxyp-chlorodiethyl ether. It is a colorless oil boiling at200 to 205 C./3 mm.

In a similar manner, the corresponding bromo ether or iodo ether can beemployed, in which case the heating with sodium sulphite can be carriedout under a reflux condenser at atmospheric pressure.

' Example 3 SOaK To g. of p-ter-octylphenoxy-isopropoxyisopropylchloride (a liquid boiling at to C./5 mm., made fromp,fl'-dichlorodiisopropyl ether, caustic soda, andp-a,a,-y,'y-tetramethylbutyl phenol), 60 g. of chlorosulphonic acid isadded while cooling to 5 to 10 C. and stirring rapidly. After eighthours at 10 to 15 C. the mixture is allowed to come to room temperatureand is neutralized with 10% potassium hydroxide solution. This solutionis placed in an iron autoclave and heated at 160 to 170 C. for sevenhours, with 66 g. of sodium sulphite (95% purity) and 270 cc. of water,during which time the pressure developed is 140-150 lbs. per squareinch. The solution obtained isuseful as a cleansing or emulsifyingagent.

A compound having the above composition is obtained by condensing equalweights of cetyl alcohol, phenol and zinc chloride for eighteen Example4 CHI-GHQ c, 0HQo-omcm-o-cmom-smm OH on r OtNB Example 5omi-cnOo-onl-cm-o-oar-om-solx I SOaNa 60 g. of chlorosulphonic acid isadded dropwise to 145 g. of p-benzylphenoxyethoxyethyl chloride, whilestirring and keeping the temperature at 5 to 10 C. After addition iscomplete, stirring is continued for four hours at 20 to 25 C., and thereddish product neutralized with 10% caustic soda solution. The productis then mixed with 83 g. of anhydrous potassium sulphite purity) and 180cc. of water, and heated in an autoclave for six hours at 165 to 170 C.The product is useful as a penetrant for cellulose.

Example 6 some 60 g. of chlorosulphonic acid is added at 5 to 10 C. to184 g. of dodecylphenoxyethoxyethyl chloride (a colorless oil, B. P.185-200/4 mm., made from fl,fi'-dichlorodiethyl ether, and the mixeddodecylphenols obtained by heating technical lauryl alcohol and phenolwith zinc chloride at 190 to 200 C. for sixteen to twenty-four hours)and the mixture stirred for eight hours at 15 to 20 C. The sulphonationproduct is then neutralized with dilute caustic soda and heated underpressure at 180 to 190 C. for eight hours with a mixture of 66 g. ofanhydrous sodium sulphite (95%) and 280 cc. of water. The soaplikeproduct obtained is treated with dilute hydrochloric acid until alltraces of sulphite are destroyed, and then neutralized with caustic sodato pH 7. This product is a very effective emulsifying and cleansingagent.

hours at 190 to 200 C., and after washing out the zinc chloride, andremoving unchanged phenol by fractionation, heating the residual oil foreight hours at .to C. with one and onehalf times its weight ofp,p'-dichlorodiethyl ether and 0.30 of its weight of 50% caustic sodasolution. The resulting cetylph'enoxyethoxyethyl chloride is separatedby vacuum distillation. It forms a pale yellow to colorless oil, boilingat 250 to 270 C./2 mm. This material is sulphonated with one-third itsweight of chlorosulphonic acid at 10 to 20 C. for eight hours, and

neutralized with 10% caustic soda solution. Sodium sulphite equal toone-third of the weight of the cetyl phenoxyethoxyethyl chloride is thenadded. The solution thus obtained is diluted with an equal volume ofwater and heated under pressure, with stirring, for eight hours at 180to 190 C.

The resultant product is a powerful detergent and emulsifying agent.

By the same procedure, stearylphenol is converted tostearyl-phenoxyethoxyethyl chloride. This is sulphonated as above,neutralized with caustic alkali, and heated with an equivalent quantityof alkali metal sulphite under pressure at 180 to 190 C.

The sulphonated stearylphenoxyethoxyethyl sulphonate in the form of itssodium or potassium salt is a soap-like material having powerfuldetergent properties.

Example 8 SOJNa A mixture consisting of 86 g. decanoic acid, 188 g.

phenol, and 34 g. boron trifluoride was heated, with stirring under areflux condenser for 2 hours at -160 C. The product was washed with hotwater and distilled in vacuo. Seventy-six g. of decanoylphenols wereobtained, B. P. 184-220/4 mm. A mixture of 62 g. of this decanoylphenoland 143 g. of p,;8-dichlorodiethyl ether, 11.! g. sodium hydroxide, and15 cc. water, was heated for 6 hours at 110-115 C. under reflux, withgood agitation. After removing the sodium chloride, the product wasfractionated in vacuo, yielding 50 g. of decanoylphenoxyethoxyethylchloride. as a pale yellow oil, B. P. 220-240 C./4

To 44 g. of decanoylphenoxyethoxyethyl chloride there was added dropwise15.2 g. of chlorsulphonic acid, while stirring and cooling to 5 C. After12 hours at room temperature, the. sulphonation product. was dilutedwith 100 cc. of

V water and neutralized with aqueous 10% sodium hydroxide solution. Itwas then mixed with 16.5 g. NazSOs and 100 cc. of water, and heated inan iron autoclave with stirring for six hours at 180-490 C. The soapysolution obtained was pounds. I

Example 9 Cetyl NaSOa- -'--ooH,cmo-crr,cmsoli-ia SOaNa To 212 g. ofcetylphenoxyethoxyethyl chloride there was added dropwise at 5 to 10 C.,with constant stirring, 120 g. of chlorosulphonic acid. The mixture wasstirred eight hours at 10 to 15 C., then at 25 to 30 C. for eight hoursmore. The product was neutralized with 5% caustic soda solution, thenmixed with 66 g. of sodium sulphite (95%), and heated under pressure at170 to 180 C. for six hours. The resultant aqueous solution showspowerful detergent action.

Example 10 To 45 g. of octadecylphenoxyethoxyethyl chloride (a colorlessoil, B. P. 240-270 C./4 mm., prepared from p,p-dichlorodiethyl ether,sodium hydroxide and the octadecylphenols derived by heating equalweights of n-octa-decanol, phenol, and anhydrous zinc chloride at 185 C.for 18 hours) there was added dropwise 12 g. chlorsulphonic acid, whilestirring and cooling to 5 C. The mixture was stirred for 12 hours at20-25 C., and then neutralized with 10% aqueous potassium hydroxide. Thesoapy solution thus obtained was mixed with 16 g. anhydrous sodiumsulphite,

cc. water, and heated with stirring in an iron autoclave at 180-190 C.,for six hours. The product was treated with dilute hydrochloric acid todestroy traces of sulphite, adjusted to a pH 8, filtered, and evaporatedto dryness. A white powder was obtained having a high degree ofwater-solubility and useful as an emulsifying and cleansing agent.

Example 11 In the manufacture of synthetic methanol by the action ofhydrogen on carbon monoxide at high pressures in the presence ofcatalysts, there are obtained higher aliphatic primary and secondaryalcohols having branched chains. A fraction of such alcohols boiling at160-200 C. contains branched chain primary and secondary octyl-, nonyl-,decyl-, undecyl-, and possibly higher alcohols. Such a fraction wascondensed at 185 C. with an equal weight of phenol and anhydrous zincchloride for 18 hours while stirring under reflux. The mixedalkylphenols obtained boiled at 140180 C./1l mm., and consistedessentially of mixed octyl-, nonyl-, decyl-, and undecylphenols,together with some of the corresponding ethers. Upon condensation ofthese mixed phenols with p,p-dichlorodiethyl ether and sodium hydroxideat 110-115 C., the corresponding mixed chloroethoxyethyl ethers wereobtained. This is a colorless oil boiling at 170-210 C./4 mm. andcontaining 10.6% chlorine by analysis.

156 g. of this material was sulphonated at 10 C. with 61 g. ofchlorsulphonic acid and neutralized with a 10% solution of sodiumhydroxide. The resulting soapy solution was then mixed with g. sodiumsulphite purity) and 200 cc. of water, and heated at 180-190 C. in aniron autoclave for 8 hours. The resulting solution is a powerfulwetting, dispersing and cleansing agent Example 12 A mixture consistingof 124 g. 5-ethyl-nonanol-2, 124 g. phenol, and 124 g. anhydrous zincchloride was boiled while stirring under reflux for 18 hours. Theproduct was washed with water and fractionated in vacuo, yielding g. ofan undecylphenol fraction boiling at 146-156 C./2 mm.

This product was condensed with excess 3,3-

dichlordiethyl ether, and one mol. equivalent of caustic soda at 100110C. for 8 hours, to yield fi-undecylphenoxy-p-chlorodiethyl ether,boiling at 200-215 C./5 mm.

70.9 g. of the above chloroether was sulfonated with 24.3 g. ofchlorsulphonic acid at 5-10 C. for hour, then stirred for- 18 hours atroom temperature, and neutralized with 10% sodium hydroxide solution.The aqueous solution obtained was mixed with 26 g. NazSO: and heated inan iron autoclave at 180-l90 C. while stirringfor 6-3 hours. The soapysolution obtained was warmed with dilute acetic acid to destroysulphites, neutralized and evaporated to dryness. Product was a white,water-soluble powder, having detergent and emulsifying properties.

The reactions herein described are applicable to all aryloxypolyalkyleneether halides of the general formula herein set forth.

As further examples of the chlorides which may be used in the presentinvention, the following are given, together with their physicalconstants.

B- (s-naphthoxy) 3'-chlorodiethyl ether. 011.

B .P. 215 C./l0 mm. e (o benzylphenoxy) B chlorodiethyl ether.

Oil. B. P. 230-233/l0 mm. B-(o-cyclohexylphenoxy) 3' chlorodiethylether.

Oil. B. P. 206-209/l0 mm.

19 (o phenylphenoxy) ,3 chlorodiethyl ether.

Oil. B. P. 211-213/10 mm.

B- (p-phenylphenoxy) -,6'-chlorodiethyl e t h e r.

Solid. M. P. 51 C.

p-thymoxy-fl-chlorodiethyl ether. Oil. B. P.'

176-178/10 mm. 5- (3,5-'dimethylphenoxy) -B'-chlorodiethyl ether.

Oil. B. P. 168/10 mm.

B. P. 148-151 C./4 mm. B p-ter-butylphenoxyethoxy) -p'-chlorodiethyether. Oil. B. P. -168/3 mm. s (p-ter-amylphenoxyethoxy) -p'-chlorodiethyl ether. Oil. B. P. 189-19l/4 mm.

fi p nitrophenoxyethoxy) -'p" chlorodiethyl ether. Oil. B. P. 213-215/2mm.

s o benzylphenoxyethoxy) flchlorodiethyl ether. Oil. B. P. 205-208/3 mm.fl chlorophenoxyethoxy) fl chlorodiethyl ether. Oil. B. P. l65-171/3 mm.

18 (o methoxyphenoxyethoxy) -;9-chlorodiethyl ether. Oil. B. P.165-1'70/3 mm. p-thymoxyethoxy-p'-chlorodiethyl ether.

B. P. 171174/3 mm. p-p-cresyloxyethoxy-fi'-chlorodiethyl ether. Oil.

B. P. 168-l71/3 mm.

s (2,4-dichlorophenoxyethoxy) -,B'-chlorodiethyl ether. Oil. B. P.188-193/4 mm.

p benzylphenoxyethoxy) fl -chlorodiethyl ether. Oil. B. P. 241-247/4 mm.

13 p benzoylphenoxyethoxy) -p'-chlorodiethyl ether. Oil. B. P. 250-260/3mm.

5- (p-cyclohexylphenoxyethoxy) S'-chlorodiethyl ether. Oil. B. P.198-200/3 mm.

5- (s-naphthoxyethoxy) -fl'-chlorodiethyl ether.

Oil. B. P. 207-212/3 mm.

,6 p phenylphenoxyethoxy) fl'-chlorodiethyl ether. Solid. M. P. 58 C.

It has already been proposed to sulphonate phenols of various kinds andaromatic ethers, such as laurylbenzyl ether. the compounds heretoforeproduced contains a sulphonic group in the ring as well as in thesidechain, and a plurality of ether linkages. I have found that themolecular configuration of the present compounds leads to highwater-solubility and extreme resistance to precipitation by magnesium,iron, or calcium salts. Aqueous solutions of these compounds, especiallythose having eight to eighteen carbon atoms in the alkyl or acyl group,cause a very great lowering of the surface tension as well as of theinterfacial tensions against oils. They have high spreadingcoefficients, and high swelling and penetration values.

They may be added to dye baths to promote even dyeing, or to causticmercerizing baths to assist penetration. They are useful as spreadersfor insecticides, wetting agents for sulphur, zinc oxide, clays,Portland cement, and various pigments. When used in conjunction withhard water and ordinary soaps, they prevent the precipitation of calciumand magnesium soaps, and in case any such have been formed, willredisperse the precipitate, thus preventing it from staining fabricswhich are being dyed or cleaned. In the acidic form they may becondensed with aldehydes such as formaldehyde, to yield complexwater-soluble materials, useful as tanning agents for leather.

I claim: 1

1. A compound of the general formula i i-o-m'som $03M in which R is anaromatic group, R a polyalkylene ether radical, and M is a member of thegroup consisting of hydrogen and alkali metals. 2. A water-soluble saltof a compound which, in the acidic form, has the general formula.

li-O-(C nH2n 0 =C H2nSOaH, 9

However, none of wherein n, a: and y are small integers, n being 2to3;xis 1to2; ybeing 1to2; andRisanaromatic nucleus of the benzene andnaphthalene series which can contain as a nuclear substituent a memberof the group consisting of hydrocarbon, acyl, halogen, alkoxy, and nitrogroups; CnH2n being an alkylene group in which at least two carbon atomsseparate alternate ether oxygen atoms O; said salt being a member of thegroup consisting of alkali metal, ammonium and amine salts.

3. An alkali metal salt of a polysulphonic acid having the generalformula wherein a: and y are small integers, a: is 1 to 2; 11 being 1 to2; and R is an aromatic nucleus of the benzene and naphthalene series,which can contain as a nuclear substituent a member of the groupconsisting of hydrocarbon, acyl, halogen, alkoxy and nitro groups.

4. An alkali metal salt of a polysulphonic acid having the generalformula wherein :n is 1 to 2, and A is an aliphatic openchain radical.

5. An alkali metal salt of a polysulphonic acid having the generalformula wherein A is an alkyl group containing from 8 through 18 carbonatoms.

6. The compound 7. A process of preparing a compound of the generalformula in which R is an aromatic group, R a polyalkylene ether radical,and Ma member ofthe group consisting of hydrogen and alkali metals,which comprises treating a compound of the general formula R-O-R Cl witha member of the group consisting of concentrated and fuming sulphuricacid, chlorsulphonic acid and sulphur trioxide to sulphonate thearomatic group, neutralizing the sulphonic acid thus formed with analkali metal hydroxide and thereafter heating the resulting salt with analkali metal sulphite to split out the alkali metal chloride. I 8. Aprocess for preparing compounds which, in the acidic form, have thegeneral formulawherein n, as, and y are small integers, n being 2 to 3;a: is 1 to 2; y being 1 to 2, andR is an arcmatic nucleus of the benzeneand naphthalene series, CnH2n being an alkylene group in which at leasttwo carbon atoms separate alternate wherein n, x and 1 are smallintegers, n being 2to3;xis1to2,ybeing1to2,andRisan aromatic nucleus ofthe benzene and naphthalene series, CnH2n being an alkylene group inwhich at least two carbon atoms separate alternate ether oxygen atoms;which comprises treating a compound of the general formulaR0-C1|H2nO-):'CaH2nCl with at least one equivalent of chlorsulphonicacid so as to sulphonate R, neutralizing the sulphonic acid thus formedwith an alkali metal base, and heating the resultant salt in anautoclave with an aqueous solution of an alkali metal sulphite to atemperature between 130 and 190 C. so as to split out alkali metalchloride.

10. A process for preparing capillary-active substances, which comprisessulphonating the aromatic ring of a compound having the formula whereinA is an aliphatic open-chain radical which is a member oi! the groupconsisting of alkyl and acyl radicals having at least 8 carbon atoms, 11is 2 to 3, and x is 1 to 2; neutralizing the sulphonic acid formed withan alkali metal base, and heating the product with an alkali metalsulphite so as to split out alkali metal chloride.

HERMAN A. BRUBON.

